CN114620766B - Comprehensive utilization method of water quenched titanium-containing blast furnace slag - Google Patents
Comprehensive utilization method of water quenched titanium-containing blast furnace slag Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 61
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 61
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000002893 slag Substances 0.000 title claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000002386 leaching Methods 0.000 claims abstract description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 52
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000706 filtrate Substances 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- 239000012065 filter cake Substances 0.000 claims abstract description 27
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 27
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 27
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 26
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 25
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000003337 fertilizer Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000012452 mother liquor Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 14
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 13
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 13
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000498 cooling water Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims 1
- 230000000171 quenching effect Effects 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 7
- 238000000227 grinding Methods 0.000 description 6
- 239000010413 mother solution Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C1/00—Ammonium nitrate fertilisers
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a comprehensive utilization method of water quenched titanium-containing blast furnace slag, belonging to the technical field of recycling of water quenched titanium-containing blast furnace slag; the method comprises the following steps: s1, carrying out pressurized acid leaching on water quenched titanium-containing blast furnace slag, nitric acid and water, wherein the mass ratio of the water quenched titanium-containing blast furnace slag to the nitric acid to the water is 1 (1-2) (1.5-4), and the ratio of slag to liquid is 1:2-5; s2, cooling the slurry obtained in the step S1, and then performing liquid-solid separation to obtain filtrate and a filter cake; s3, washing and drying the filter cake obtained in the step S2, and reacting with sulfuric acid to prepare a titanium dioxide precursor; s4, neutralizing the filtrate obtained in the step S2 with ammonia water to recover iron, aluminum and vanadium, and obtaining mother liquor; s5, evaporating, concentrating and crystallizing the mother liquor obtained in the step S4 to prepare the calcium-magnesium-containing ammonium nitrate fertilizer. The invention realizes the whole waste recycling and has high titanium element extraction rate; the process is simple to operate and the equipment investment is low.
Description
Technical Field
The invention relates to the technical field of recycling of water quenched titanium-containing blast furnace slag, in particular to a comprehensive utilization method of water quenched titanium-containing blast furnace slag.
Background
The titanium-containing blast furnace slag is industrial solid waste produced by smelting vanadium titano-magnetite in the blast furnace, and is prepared by TiO in the blast furnace slag 2 The high titanium blast furnace slag (w (TiO) 2 ) More than 16 percent, and medium titanium blast furnace slag (10 percent is less than or equal to w (TiO) 2 ) Less than or equal to 15 percent) and low titanium blast furnace slag (w (TiO) 2 ) < 10%) since it has not been foundThe method for efficiently and comprehensively utilizing the titanium-containing blast furnace slag causes the titanium-containing blast furnace slag to be accumulated in a large amount, occupies a large area of land, damages vegetation, pollutes soil and water, can cause natural disasters such as debris flow, dust and the like especially under severe weather conditions, and aggravates the pollution of surrounding environments.
At present, there are only two methods for treating titanium-containing blast furnace slag. One is to make titanium-containing blast furnace slag into a certain material for integral use, and the other is to carry out titanium extraction treatment. In recent decades, a great deal of research work has been done on the utilization of high-titanium blast furnace slag resources, mainly on the aspects of extracting titanium pigment from the high-titanium blast furnace slag, preparing titanium-containing alloy and titanium compound, preparing photocatalyst and antibacterial material, synthesizing conductive ceramic, preparing fertilizer and the like.
CN103952567a mentions a method for recovering titanium, silicon, aluminum, calcium and magnesium from titanium-containing blast furnace slag by using multi-stage acid leaching, wherein the acid leaching agent is hydrochloric acid, and the leaching is divided into 3-6 stages, so that the process flow is long, and the elements are difficult to separate in the later stage.
In CN111333108A, titanium in the titanium-containing blast furnace slag is extracted by utilizing the acidity and complexation of an organic acid, so that titanium dioxide is produced, and other elements in the titanium-containing blast furnace slag are not effectively utilized.
Disclosure of Invention
The invention aims to solve the technical problem of providing a comprehensive utilization method of water quenched titanium-containing blast furnace slag, which can be used for carrying out pressure leaching on impurity elements in the titanium-containing blast furnace slag, then carrying out liquid-solid separation, preparing a titanium sulfate white raw material by using an obtained filter cake, recovering iron, aluminum and vanadium from the obtained filtrate, and then using the obtained filtrate as a fertilizer, thereby realizing the whole waste material.
In order to solve the technical problems, the invention provides the following technical scheme:
a comprehensive utilization method of water quenched titanium-containing blast furnace slag comprises the following steps:
s1, carrying out pressurized acid leaching on water quenched titanium-containing blast furnace slag, nitric acid and water, wherein the mass ratio of the water quenched titanium-containing blast furnace slag to the nitric acid to the water is 1 (1-2) (1.5-4), the ratio of slag to liquid is 1:2-5, and the concentration of the nitric acid is 50-70 wt%;
the conditions of the pressurized acid leaching include: the acid leaching temperature is 160-210 ℃ and the pressure is 0.4-1.5 MPa;
s2, cooling the slurry obtained in the step S1, and then performing liquid-solid separation to obtain filtrate and a filter cake;
s3, washing and drying the filter cake obtained in the step S2, and reacting with sulfuric acid to prepare a titanium dioxide precursor;
s4, neutralizing the filtrate obtained in the step S2 with ammonia water to recover iron, aluminum and vanadium, and obtaining mother liquor; wherein ammonia water is firstly adjusted to pH 3-4 to precipitate and recycle iron, then adjusted to pH 6-7 to recycle aluminum, and then adjusted to pH 9-12 to recycle vanadium;
s5, evaporating, concentrating and crystallizing the mother liquor obtained in the step S4 to prepare the calcium-magnesium-containing ammonium nitrate fertilizer.
Wherein, preferably, the titanium dioxide content in the water quenched titanium-containing blast furnace slag is more than 20wt%, the calcium oxide content is more than 20wt%, the magnesium oxide content is more than 10wt%, and the aluminum oxide content is more than 10 wt%.
Wherein, preferably, in step S1, the conditions of the pressurized acid leaching further include: the stirring speed is 400-500 r/min, and the pickling time is 1-5 h.
Preferably, in step S2, the cooling manner includes: and under the condition of pressurization, firstly cooling the material temperature in a reaction kettle adopted by the pressurized acid leaching to 50-80 ℃ by using cooling water, then evacuating, and finally pouring out slurry.
Preferably, the comprehensive utilization method further comprises: and (3) preparing rutile titanium dioxide by hydrolyzing and calcining the titanium dioxide precursor.
Wherein, preferably, in step S3, the number of times of washing is such that the washing liquid is neutral.
In the step S2, preferably, the liquid-solid separation is suction filtration.
Wherein, in the step S3, the concentration of the sulfuric acid is preferably 85-98wt%.
The technical scheme of the invention has the following beneficial effects:
in the scheme, the pressurizing and acid leaching reaction is carried out under the specific conditions and at the low temperature, so that impurities can be sufficiently removed, the grade of titanium dioxide in a solid phase can be improved, titanium loss can not be caused by acid leaching of titanium-containing blast furnace slag by nitric acid, and the impurity removing effect is obvious. And the calcium-magnesium-containing ammonium nitrate fertilizer is prepared by combining with ammonia water precipitation to recycle impurity elements and simultaneously carrying out combined evaporation concentration crystallization. Wherein the nitrogen in the nitric acid forms ammonium nitrate in the final fertilizer without consumption or waste. The whole process is simple to operate and has less equipment investment.
Detailed Description
The invention provides a comprehensive utilization method of water quenched titanium-containing blast furnace slag, which comprises the following steps:
s1, carrying out pressurized acid leaching on water quenched titanium-containing blast furnace slag, nitric acid and water, wherein the mass ratio of the water quenched titanium-containing blast furnace slag to the nitric acid to the water is 1 (1-2) (1.5-4), the slag-liquid ratio is 1:2-5, and the concentration of the nitric acid is 50-70 wt%, and can be specifically any value of 50, 55, 60, 65 and 70wt% or any value between adjacent point values;
the conditions of the pressurized acid leaching include: the acid leaching temperature is 160-210 ℃ and the pressure is 0.4-1.5 MPa;
s2, cooling the slurry obtained in the step S1, and then performing liquid-solid separation to obtain filtrate and a filter cake;
s3, washing and drying the filter cake obtained in the step S2, and reacting with sulfuric acid to prepare a titanium dioxide precursor;
s4, neutralizing the filtrate obtained in the step S2 with ammonia water to recover iron, aluminum and vanadium, and obtaining mother liquor; wherein ammonia water is firstly adjusted to pH 3-4 to precipitate and recycle iron, then adjusted to pH 6-7 to recycle aluminum, and then adjusted to pH 9-12 to recycle vanadium;
s5, evaporating, concentrating and crystallizing the mother liquor obtained in the step S4 to prepare the calcium-magnesium-containing ammonium nitrate fertilizer.
Wherein, preferably, the titanium dioxide content in the water quenched titanium-containing blast furnace slag is more than 20wt%, the calcium oxide content is more than 20wt%, the magnesium oxide content is more than 10wt%, and the aluminum oxide content is more than 10 wt%.
In the step S1, nitric acid is particularly adopted to match with specific leaching conditions, so that the loss of titanium is avoided, and the extraction rate of titanium is improved. Under the same conditions, if titanyl sulfate is produced by acid leaching with sulfuric acid, titanyl chloride is produced by acid leaching with hydrochloric acid, which leads to titanium loss.
The nitric acid used in the invention is finally recycled to prepare ammonium nitrate, the amount of nitric acid is not consumed in the whole acid leaching process, and the preparation process is simple.
Wherein, in the step S3, the concentration of the sulfuric acid is preferably 85-98 wt%, and can be specifically any point value of 80, 85, 90 and 99wt% or any value between adjacent point values; more preferably 90 to 99wt%.
Wherein, the mass ratio is 1 (1-2), 1-2 in (1.5-4) can be any value in 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 and 2 and any value between two adjacent point values; 1.5 to 4 may be, for example, any value among 1.5, 2, 2.6, 3, 3.5, 4 and any value between two adjacent dot values.
The slag-liquid ratio is 1:2-5, and can be any value among 2, 2.5, 3, 3.5, 4, 4.5 and 5 and any value between two adjacent point values.
The acid leaching temperature is 160-210 ℃, and can be any value of 160, 165, 170, 175, 200 and 210 ℃ and any value between two adjacent points.
The pressure is 0.4 to 1.5MPa, and may be any value among 0.4, 0.5, 0.7, 1, 1.2, and 1.5MPa, and any value between two adjacent point values, for example.
Wherein, preferably, in step S1, the conditions of the pressurized acid leaching further include: the stirring speed is 400-500 r/min, and the pickling time is 1-5 h.
The stirring rotation speed is 400-500 r/min, and can be any value among 400, 420, 430, 440, 450, 470 and 500r/min and any value between two adjacent point values.
The acid leaching time is 1 to 5 hours, and can be any value among 1, 2, 3, 4 and 5 hours and any value between two adjacent point values.
Preferably, in step S2, the cooling manner includes: and under the condition of pressurization, firstly cooling the material temperature in a reaction kettle adopted by the pressurized acid leaching to 50-80 ℃ by using cooling water, then evacuating, and finally pouring out slurry.
Preferably, in step S2, the liquid-solid separation is performed by suction filtration.
Preferably, the comprehensive utilization method further comprises: and (3) preparing rutile titanium dioxide by hydrolyzing and calcining the titanium dioxide precursor. The conditions of hydrolysis and calcination can be carried out by adopting the existing conditions, so long as the preparation of rutile titanium dioxide can be facilitated.
Wherein, preferably, in step S3, the number of times of washing is such that the washing liquid is neutral. In the preferred scheme, the acid and impurity ions mixed in the filter cake can be sufficiently washed, and the purity of titanium in the filter cake is further improved.
In order to make the technical problems, technical solutions and advantages to be solved by the present invention more apparent, the following detailed description will be made with reference to specific embodiments. The water quenched titanium-containing blast furnace slag (titanium-containing blast furnace slag for short) used in the examples had a titanium dioxide content of 20% or more, a calcium oxide content of 25%, a magnesium oxide content of 10% and an aluminum oxide content of 17% by mass. In the examples below, nitric acid refers to technical nitric acid (at a concentration of 60 wt%) and sulfuric acid refers to technical sulfuric acid (at a concentration of 98 wt%).
Example 1
After 100g of titanium-containing blast furnace slag, 100g of nitric acid and 150g of titanium-containing blast furnace slag are respectively added into a 2L pressurized reaction kettle, a cover is added, the stirring bearing cooling water, the stirring and the heating jacket are sequentially started for heating, the temperature is slowly raised from the room temperature, the reaction is carried out for 2 hours, the reaction temperature is 160 ℃, the pressure is 0.4MPa, the rotating speed is 500r/min, the coil cooling water in the reaction kettle is started after the reaction is finished, when the temperature in the kettle is reduced to 60-80 ℃, an emptying port is opened for emptying, and the slurry is sequentially poured out for solid-liquid separation, so that filtrate and filter cake are obtained. And (3) analyzing filtrate to obtain: the leaching rate of iron is 70%, the leaching rate of aluminum is 80%, the leaching rate of vanadium is 85%, the leaching rate of calcium is 90%, and the leaching rate of magnesium is 85%.
Washing the filter cake with 100ml of water for 2 times, drying, grinding, and reacting with sulfuric acid to prepare the titanyl sulfate, wherein the extraction rate of the titanium is 85%.
Neutralizing the filtrate with ammonia water to recover iron, aluminum and vanadium to obtain mother liquor; wherein the ammonia water is firstly adjusted to pH 3-4 to precipitate and recycle iron, then adjusted to pH 6-7 to recycle aluminum, and then adjusted to pH 9-12 to recycle vanadium. Evaporating, concentrating and crystallizing the mother solution to prepare the calcium-magnesium-containing ammonium nitrate fertilizer.
Example 2
After 100g of titanium-containing blast furnace slag, 120g of nitric acid and 150g of nitric acid are respectively added into a 2L pressurized reaction kettle, a cover is added, the stirring bearing cooling water, the stirring and the heating jacket are sequentially started for heating, the temperature is slowly raised from the room temperature, the reaction is carried out for 3 hours, the reaction temperature is 160 ℃, the pressure is 0.4MPa, the rotating speed is 500r/min, the coil cooling water in the reaction kettle is started after the reaction is finished, when the temperature in the kettle is reduced to 60-80 ℃, an emptying port is opened for emptying, and the slurry is sequentially poured out for solid-liquid separation, so that filtrate and filter cake are obtained. And (3) analyzing filtrate to obtain: the leaching rate of iron is 80%, the leaching rate of aluminum is 90%, the leaching rate of vanadium is 95%, the leaching rate of calcium is 95%, and the leaching rate of magnesium is 90%.
Washing the filter cake with 100ml of water for 2 times, drying, grinding, and reacting with sulfuric acid to prepare titanyl sulfate, wherein the extraction rate of titanium is 90%.
Neutralizing the filtrate with ammonia water to recover iron, aluminum and vanadium to obtain mother liquor; wherein the ammonia water is firstly adjusted to pH 3-4 to precipitate and recycle iron, then adjusted to pH 6-7 to recycle aluminum, and then adjusted to pH 9-12 to recycle vanadium. Evaporating, concentrating and crystallizing the mother solution to prepare the calcium-magnesium-containing ammonium nitrate fertilizer.
Example 3
After 100g of titanium-containing blast furnace slag, 150g of nitric acid and 150g of nitric acid are respectively added into a 2L pressurized reaction kettle, a cover is added, the stirring bearing cooling water, the stirring and the heating jacket are sequentially started for heating, the temperature is slowly raised from the room temperature, the reaction is carried out for 3 hours, the reaction temperature is 180 ℃, the pressure is 0.7MPa, the rotating speed is 500r/min, the coil cooling water in the reaction kettle is started after the reaction is finished, when the temperature in the kettle is reduced to 60-80 ℃, an emptying port is opened for emptying, and the slurry is sequentially poured out for solid-liquid separation, so that filtrate and filter cake are obtained. And (3) analyzing filtrate to obtain: the leaching rate of iron is 85%, the leaching rate of aluminum is 95%, the leaching rate of vanadium is 96%, the leaching rate of calcium is 98%, and the leaching rate of magnesium is 92%.
Washing the filter cake with 100ml of water for 2 times, drying and grinding the filter cake, and reacting with sulfuric acid to prepare titanyl sulfate, wherein the extraction rate of titanium is 91%.
Neutralizing the filtrate with ammonia water to recover iron, aluminum and vanadium to obtain mother liquor; wherein the ammonia water is firstly adjusted to pH 3-4 to precipitate and recycle iron, then adjusted to pH 6-7 to recycle aluminum, and then adjusted to pH 9-12 to recycle vanadium. Evaporating, concentrating and crystallizing the mother solution to prepare the calcium-magnesium-containing ammonium nitrate fertilizer.
Example 4
After 100g of titanium-containing blast furnace slag, 150g of nitric acid and 200g of titanium-containing blast furnace slag are respectively added into a 2L pressurized reaction kettle, a cover is added, the stirring bearing cooling water, the stirring and the heating jacket are sequentially started for heating, the temperature is slowly raised from the room temperature, the reaction is carried out for 3 hours, the reaction temperature is 180 ℃, the pressure is 0.8MPa, the rotating speed is 500r/min, the coil cooling water in the reaction kettle is started after the reaction is finished, when the temperature in the kettle is reduced to 60-80 ℃, an emptying port is opened for emptying, and the slurry is sequentially poured out for solid-liquid separation, so that filtrate and filter cake are obtained. And (3) analyzing filtrate to obtain: the leaching rate of iron is 84%, the leaching rate of aluminum is 92%, the leaching rate of vanadium is 93%, the leaching rate of calcium is 92%, and the leaching rate of magnesium is 88%.
Washing the filter cake with 100ml of water for 2 times, drying and grinding the filter cake, and reacting with sulfuric acid to prepare the titanyl sulfate, wherein the extraction rate of the titanium is 89%.
Neutralizing the filtrate with ammonia water to recover iron, aluminum and vanadium to obtain mother liquor; wherein the ammonia water is firstly adjusted to pH 3-4 to precipitate and recycle iron, then adjusted to pH 6-7 to recycle aluminum, and then adjusted to pH 9-12 to recycle vanadium. Evaporating, concentrating and crystallizing the mother solution to prepare the calcium-magnesium-containing ammonium nitrate fertilizer.
Example 5
After 100g of titanium-containing blast furnace slag, 165g of nitric acid and 235g of titanium-containing blast furnace slag are respectively added into a 2L pressurized reaction kettle, a cover is added, the stirring bearing cooling water, the stirring and the heating jacket are sequentially started for heating, the temperature is slowly raised from the room temperature, the reaction is carried out for 3 hours, the reaction temperature is 200 ℃, the pressure is 1.3MPa, the rotating speed is 500r/min, the coil cooling water in the reaction kettle is started after the reaction is finished, when the temperature in the kettle is reduced to 60-80 ℃, an emptying port is opened for emptying, and the slurry is sequentially poured out for solid-liquid separation, so that filtrate and filter cake are obtained. And (3) analyzing filtrate to obtain: the leaching rate of iron is 85%, the leaching rate of aluminum is 96%, the leaching rate of vanadium is 98%, the leaching rate of calcium is 97%, and the leaching rate of magnesium is 93%.
Washing the filter cake with 100ml of water for 2 times, drying and grinding the filter cake, and reacting with sulfuric acid to prepare titanyl sulfate, wherein the extraction rate of titanium is 95%.
Neutralizing the filtrate with ammonia water to recover iron, aluminum and vanadium to obtain mother liquor; wherein the ammonia water is firstly adjusted to pH 3-4 to precipitate and recycle iron, then adjusted to pH 6-7 to recycle aluminum, and then adjusted to pH 9-12 to recycle vanadium. Evaporating, concentrating and crystallizing the mother solution to prepare the calcium-magnesium-containing ammonium nitrate fertilizer.
Example 6
After 100g of titanium-containing blast furnace slag, 135g of nitric acid and 265g of titanium-containing blast furnace slag are respectively added into a 2L pressurized reaction kettle, a cover is added, the stirring bearing cooling water, the stirring and the heating jacket are sequentially started for heating, the temperature is slowly raised from the room temperature, the reaction is carried out for 3 hours, the reaction temperature is 200 ℃, the pressure is 1.3MPa, the rotating speed is 500r/min, the coil cooling water in the reaction kettle is started after the reaction is finished, when the temperature in the kettle is reduced to 60-80 ℃, an emptying port is opened for emptying, and the slurry is sequentially poured out for solid-liquid separation, so that filtrate and filter cake are obtained. And (3) analyzing filtrate to obtain: the leaching rate of iron is 83%, the leaching rate of aluminum is 92%, the leaching rate of vanadium is 95%, the leaching rate of calcium is 96%, and the leaching rate of magnesium is 90%.
Washing the filter cake with 100ml of water for 2 times, drying and grinding the filter cake, and reacting with sulfuric acid to prepare titanyl sulfate, wherein the extraction rate of the titanium is 92%.
Neutralizing the filtrate with ammonia water to recover iron, aluminum and vanadium to obtain mother liquor; wherein the ammonia water is firstly adjusted to pH 3-4 to precipitate and recycle iron, then adjusted to pH 6-7 to recycle aluminum, and then adjusted to pH 9-12 to recycle vanadium. Evaporating, concentrating and crystallizing the mother solution to prepare the calcium-magnesium-containing ammonium nitrate fertilizer.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (5)
1. The comprehensive utilization method of the water quenched titanium-containing blast furnace slag is characterized by comprising the following steps of:
s1, carrying out pressurized acid leaching on water quenched titaniferous blast furnace slag, nitric acid and water, wherein the mass ratio of the water quenched titaniferous blast furnace slag to the nitric acid to the water is 1 (1.2-2) (1.5-4), the ratio of slag to liquid is 1:3-5, and the concentration of the nitric acid is 50-70 wt%;
the conditions of the pressurized acid leaching include: the acid leaching temperature is 165-210 ℃ and the pressure is 1-1.5 MPa;
s2, cooling the slurry obtained in the step S1, and then performing liquid-solid separation to obtain filtrate and a filter cake;
s3, washing and drying the filter cake obtained in the step S2, and reacting with sulfuric acid to prepare a titanium dioxide precursor;
s4, neutralizing the filtrate obtained in the step S2 with ammonia water to recover iron, aluminum and vanadium, and obtaining mother liquor; wherein ammonia water is firstly adjusted to pH 3-4 to precipitate and recycle iron, then adjusted to pH 6-7 to recycle aluminum, and then adjusted to pH 9-12 to recycle vanadium;
s5, evaporating, concentrating and crystallizing the mother liquor obtained in the step S4 to prepare the calcium-magnesium-containing ammonium nitrate fertilizer;
the content of titanium dioxide in the water quenching titanium-containing blast furnace slag is more than 20 weight percent, the content of calcium oxide is more than 20 weight percent, the content of magnesium oxide is more than 10 weight percent, and the content of aluminum oxide is more than 10 weight percent;
in step S1, the conditions of the pressurized acid leaching further include: stirring rotation speed is 400-500 r/min, and acid leaching time is 1-5 h;
in step S2, the cooling method includes: and under the condition of pressurization, firstly cooling the material temperature in a reaction kettle adopted by the pressurized acid leaching to 50-80 ℃ by using cooling water, then evacuating, and finally pouring out slurry.
2. The comprehensive utilization method according to claim 1, further comprising: and (3) preparing rutile titanium dioxide by hydrolyzing and calcining the titanium dioxide precursor.
3. The comprehensive utilization method according to claim 1, wherein in step S3, the number of times of washing is made until the washing liquid is neutral.
4. The comprehensive utilization method according to claim 1, wherein in the step S2, the liquid-solid separation mode is suction filtration.
5. The comprehensive utilization method according to claim 1, wherein in the step S3, the concentration of sulfuric acid is 85 to 98wt%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037726A (en) * | 2007-04-28 | 2007-09-19 | 中南大学 | Comprehensive utilization method of titanium-containing melting furnace slag |
| CN105217664A (en) * | 2015-09-15 | 2016-01-06 | 中国科学院过程工程研究所 | A kind of titanium-containing blast furnace slag spent acid treatment and utilization method |
| CN109252056A (en) * | 2018-09-25 | 2019-01-22 | 眉山顺应动力电池材料有限公司 | A kind of processing method of low magnesium brown iron type nickel laterite ore |
| CN111498855A (en) * | 2020-04-30 | 2020-08-07 | 昆明理工大学 | Comprehensive utilization method of water-quenched high-titanium blast furnace slag |
| CN112662896A (en) * | 2020-12-18 | 2021-04-16 | 河南佰利联新材料有限公司 | Method for preparing titanium-rich material from titanium ore |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ712526A (en) * | 2013-05-17 | 2017-03-31 | Inst Process Eng Cas | Method for processing vanadium-titanium magnetite finished ores by using wet process |
-
2022
- 2022-03-14 CN CN202210249758.3A patent/CN114620766B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037726A (en) * | 2007-04-28 | 2007-09-19 | 中南大学 | Comprehensive utilization method of titanium-containing melting furnace slag |
| CN105217664A (en) * | 2015-09-15 | 2016-01-06 | 中国科学院过程工程研究所 | A kind of titanium-containing blast furnace slag spent acid treatment and utilization method |
| CN109252056A (en) * | 2018-09-25 | 2019-01-22 | 眉山顺应动力电池材料有限公司 | A kind of processing method of low magnesium brown iron type nickel laterite ore |
| CN111498855A (en) * | 2020-04-30 | 2020-08-07 | 昆明理工大学 | Comprehensive utilization method of water-quenched high-titanium blast furnace slag |
| CN112662896A (en) * | 2020-12-18 | 2021-04-16 | 河南佰利联新材料有限公司 | Method for preparing titanium-rich material from titanium ore |
Non-Patent Citations (3)
| Title |
|---|
| 邹建新等.《钒钛功能材料》.冶金工艺出版社,2019,第157-158页. * |
| 雷霆.《钛及钛合金》.冶金工艺出版社,2018,第394-397页. * |
| 非水淬高钛型高炉渣的综合利用研究;霍红英;刘国钦;邹敏;马光强;;湿法冶金(第01期);第45页左栏1.2.2酸分解液中有价成分的提取 * |
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